The nanoweb structure of TiO2 anode, cross-linked between electrospun nanofibers, is directly fabricated on the current collector by utilizing the fluidity of low glass transition temperature polymer, poly(vinyl acetate), at room temperature. This characteristic enables us to fabricate the nanoweb structure by direct electrospinning on the current collector, followed by uniaxial pressing. This proposed structure facilitates electron transport through the direct conducting pathways between TiO2 active materials and current collector as well as provides strong adhesion strength to the current collector without polymeric binders. Consequently, we could achieve stable cycle performance up to 100 cycles and the excellent rate capability of similar to 60% at high rate charge/discharge condition of 10 C.